Formulation composition for 3d additive manufacturing and processing method of the same

ABSTRACT

The present invention discloses a hybrid (mixed) formulation composition for 3D additive manufacturing and a manufacturing process. The hybrid formulation composition possesses capability of UV radiation curing and thermal curing. The hybrid formulation composition is designed to be cured by UV radiation in the 3D printing/additive manufacturing process and then post cure by heat to get its final properties. The hybrid formulation composition consists of acrylates (oligomer, monomer, and diluent), photoinitiators, and isocyanate-containing prepolymers which comprises poly-ols (di-ol, tri-ol), urea, urethane, and isocyanates. The hybrid formulation composition may also include reaction accelerator, dye, pigment, and fillers. The finished products of the hybrid formulation composition possess rubber-like properties and can be used in the applications such as shoe sole, toys, medical, and wearables goods . . . etc.

FIELD OF THE INVENTION

The present invention belongs to the field of polymer materials, andparticularly relates to a combination of a heat curing and photocurableresin composition and a preparation method thereof, which can be used inthe field of 3D additive printing.

BACKGROUND OF THE INVENTION

In conventional additive manufacturing or three-dimensionalmanufacturing techniques, three-dimensional (3D) structures areconstructed in a stepwise or layer-by-layer manner Layer formation iscarried out by curing of a photocurable resin under the action ofvisible light or ultraviolet light irradiation. The past two techniquesare known: a “top down” technique forms a new layer on the underside ofa growing object; another “bottom up” technique is on the top of agrowing object.

An early example of forming a new layer on the top surface of a growingarticle is shown in FIG. 3 of U.S. Pat. No. 5,236,637. One disadvantageof this “top down” technique is the need to immerse the growing objectin a (possibly deep) pool of liquid resin and to reconstruct a preciseliquid resin coating.

An early example of forming a new layer on the underside of a growingobject is shown in FIG. 4 of U.S. Pat. No. 5,236,637. Although this“bottom up” technique has the potential to eliminate the need for deepwells in which objects are immersed by moving the object up from arelatively shallow well or pool, such as commercially implemented Theproblem with the “bottom-up” manufacturing technique is that whenseparating the solidified layer from the substrate, extreme mechanicalcare must be used and additional mechanical components must be used dueto the physical and chemical interactions between them.

A continuous method of manufacturing 3D structures is presented quitethoroughly in the “top-down” technique in U.S. Pat. No. 7,892,474, butthis reference does not explain how they can be used in a “bottom-up”system without destroying the prepared articles. The manner ofimplementation limits the materials that can be used in the method,thereby limiting the structural properties of the object thus produced.U.S. Patent Application Publication No. 2012/0251841 describes liquidradiation curable resins for additive manufacturing, but these containcationic photoinitiators (thus limiting the materials available) and areonly recommended for additive manufacturing.

The photosensitive resin for 3D additive printing needs to be quicklycured under the exposure conditions of the 3D printer and needs to meetthe printing process of the printer and has certain fluidity. These arethe basic requirements that photosensitive resins can be used in 3Dprinters. At present, the domestic photosensitive resin used in 3Dprinters has a single variety, mainly high-hardness resins, but suchresins have the disadvantages of insufficient toughness, poor impactresistance, and brittleness. The high toughness 3D printingphotosensitive resin is new direction for printing materials

3D printing technology using photosensitive resin as printing materialmainly includes: Stereo lithography (SLA), DLP projection digital lightprocessing (DLP) and ultra-thin layer thickness photosensitive resininjection molding technology. The printing process is to establish the3D model in the computer, and then deliver the 3D printer for printing.The printing process uses ultraviolet light to irradiate the liquidphotosensitive resin and stack them layer by layer. The shortcomings ofthe photosensitive resin used in the stereolithography rapid prototyping3D printer are obvious. Due to the use of the epoxy resin with goodstability, the strength is high but very brittle, the printing model iseasily broken, and it is easy to bend and break. Increasing toughness isa requirement for stereolithography rapid prototyping 3D printingphotosensitive resin and blending with high toughness photosensitiveresin is also a solution.

Accordingly, there is a need for a hybrid formulation composition for 3Dadditive manufacturing that can be used to produce 3D structures havingsatisfactory structural properties by additive manufacturing.

SUMMARY OF THE INVENTION

The main purpose of the invention is to provide a composition formula ofa hybrid formulation composition for 3D additive manufacturing, whichcan combine ultraviolet curing and heat curing and can increase thetoughness, resilience and tear resistance of the structural materialafter curing.

Another purpose of the present invention is to provide a process for thepreparation of a mixed formulation composition for 3D additiveproduction which does not require the use of a blocked isocyanate,thereby greatly reducing the curing temperature.

Another purpose of the present invention is to provide a process forusing the hybrid formulation composition for 3D additive manufacturing,which requires only 2-3 seconds of curing, short process time, savesprocess energy and increases productivity, and can increase thetoughness, resilience and tear resistance of the structural materialafter curing.

In order to achieve the primary purpose of the present invention, thepresent invention provides a mixed formulation composition for 3Dadditive manufacturing, which mainly comprises:

-   -   A reactive isocyanate (NCO) containing prepolymer which        comprises of poly-ols (di-ol, tri-ol), urea, urethane, and        isocyanates;    -   A photocurable material formulation;    -   Optionally, a poly-ol;    -   Optionally, at least one non-reactive light absorbing pigment,        dye or photochromic material;    -   Optionally, at least one catalyst;    -   Optionally, at least one filler;        The prepolymer accounts for 0 to 80% by weight of the hybrid        formulation composition, and the poly-ols account for 10 to 30%        by weight of the hybrid formulation composition.

According to a feature of the invention, the prepolymer containingreactive isocyanate is a compound of T-R-T, R is a polymer of a polyol,each T is a terminal group of R, and T is a reactive isocyanate (NCO).

According to one feature of the invention, R in the prepolymer is morereactive end groups.

According to a feature of the invention, the prepolymer comprises apolyisocyanate oligomer produced by first reacting at least oneisocyanate with at least one polyol, and the ratio of the isocyanate tothe polyol (NCO/OH) is greater than one.

In order to achieve the secondary purpose of the present invention, thepresent invention provides a mixed formulation composition for 3Dadditive manufacturing, which mainly comprises:

-   -   Preparing a prepolymer containing reactive isocyanate;    -   Preparing a photocurable material formulation;    -   Mixing the prepolymer with the photocurable material        formulation;    -   Optionally, mixing a poly-ol, a reactive diluent, at least one        non-reactive light absorbing pigment, a dye or photochromic        material, at least one catalyst and at least one filler;    -   The prepolymer accounts for 0 to 80% by weight of the hybrid        formulation composition, and the poly-ols account for 10 to 30%        by weight of the hybrid formulation composition.

According to a feature of the invention, the photocurable formulationcomprises 0 to 100% by weight of the mixed formulation composition, andthe photocurable material comprises at least: an acrylic seriesoligomer, an acrylic series monomer, and at least a photoinitiator.

According to one feature of the invention, the acrylic series ofoligomers is selected from one of the following: epoxy acrylate (EA),polyurethane acrylate (PUA), polyester acrylate (PEA), epoxy resin,unsaturated polyester, polyether acrylate, and acrylated polyacrylicresin.

According to a feature of the invention, the acrylic series monomer isselected from one of the following groups: (meth) acrylate group, vinylgroup, vinyl ether group, epoxy group.

According to a feature of the invention, the pigment, dye orphotochromic material comprises from 0 to 12% by weight of the hybridformulation composition, and the pigment, dye or photochromic materialis selected from the group consisting of organic pigments, inorganicdyes, titanium dioxide or carbon black.

According to a feature of the invention, the catalyst comprises from 0to 1% by weight of the mixed formulation composition, and the catalystis selected from the group consisting of amine catalysts and metalcatalysts.

In order to achieve the secondary purpose of the present invention, thepresent invention provides a 3D structure process method comprising thefollowing steps:

-   -   Print a 3D structure in a 3D printer using a hybrid formulation        composition;    -   During the layered printing process, a UV light is applied;    -   After stopping the layered printing process, a heating process        is performed;    -   Wherein, the hybrid formulation composition mainly comprises:        -   A prepolymer containing reactive isocyanate (NCO) which            comprises of poly-ols (di-ol, tri-ol), urea, urethane, and            isocyanates;        -   A photocurable material formulation;        -   A poly-ol;        -   Optionally, at least one non-reactive light absorbing            pigment, dye or photochromic material;        -   Optionally, at least one catalyst;        -   Optionally, at least one filler;            The prepolymer accounts for 0 to 80% by weight of the hybrid            formulation composition, and the poly-ols account for 10 to            30% by weight of the hybrid formulation composition.

According to a feature of the invention, the UV light has a wavelengthbetween 240 nanometers (nm) and 450 nanometers (nm).

According to a feature of the invention, the UV light has an intensityof between 0.1 J/cm² and 1 J/cm².

According to a feature of the invention, the irradiation time of the UVlight is between 0.5 seconds and 90 seconds.

According to a feature of the invention, the temperature of the heatingprocess is between 50° C. and 150° C.

According to a feature of the invention, the heating process is between30 minutes and 16 hours.

The ratio of the isocyanate to the polyol (NCO/OH) of the hybridformulation composition for the 3D additive manufacturing of the presentinvention is greater than 1. (i.e. isocyanates are not blocked). Theinvention has the following effects

-   1. The toughness, resilience and tear resistance of the hybrid    formulation composition for 3D additive manufacturing can be    adjusted according to requirements, and it is free of volatile    substances, and is a very environmentally friendly and    environmentally friendly material.-   2. The hybrid formulation composition for 3D additive manufacturing    has rubber-like properties, which can increase the toughness,    resilience and tear resistance of the structural material after    curing, and can be used for shoe materials, toys, biomedical    equipment, and wearable articles.-   3. The process of the hybrid formulation composition for 3D additive    manufacturing requires only 2-3 seconds of photocuring, low heat    curing temperature, short process time, saving process energy and    increasing productivity.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other purpose, features and advantages of the presentinvention will become more apparent and understood.

FIG. 1 is a schematic view showing the process of a hybrid formulationcomposition for 3D additive manufacturing of the present invention.

FIG. 2 is a schematic view showing a first implementation flow of amethod for preparing a hybrid formulation composition for 3D additivemanufacturing according to the present invention.

FIG. 3 is a schematic view showing a second implementation flow of amethod for preparing a hybrid formulation composition for 3D additivemanufacturing according to the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

While the invention may be embodied in a variety of forms, theembodiments shown in the drawings and illustrated herein are thepreferred embodiments of the invention. Those skilled in the art willappreciate that the devices and methods specifically described hereinand illustrated in the drawings are considered as an example of theinvention, non-limiting exemplary embodiments, and the scope of theinvention defined. Features illustrated or described in connection withan exemplary embodiment may be combined with features of otherembodiments. Such modifications and variations are intended to beincluded within the scope of the invention.

Referring to FIG. 1, there is shown a process schematic diagram of amixed formulation composition for 3D additive manufacturing of thepresent invention. The present invention provides a mixed formulationcomposition for 3D additive manufacturing for preparing various 3Dstructures comprising polyurethane, polyurea, acrylic or copolymersthereof. It utilizes a 3D printer 110 to convert a hybrid formulationcomposition 120 onto a 3D structure 130 and cure the mixed compositionduring the forming process by irradiation of ultraviolet (UV) light.After the 3D structure 130 is formed, a thermal curing process can beperformed. The hybrid formulation composition can simultaneouslyincrease the toughness, resilience and tear resistance of the structuralmaterial after curing by ultraviolet curing and heat curing and istherefore referred to as a hybrid formulation composition. In thepresent invention, the amount of each component is based on the weightpercentage of the entire composition, that is, in weight %. Also, theterm “optionally” refers to a component that can be preferably selected,not necessarily.

The mixed composition 120, which mainly comprises:

A prepolymer containing reactive isocyanate (NCO) which comprises ofpoly-ols (di-ol, tri-ol), urea, urethane, and isocyanates;

-   -   a photocurable material formulation;    -   a poly-ol;    -   optionally, at least one non-reactive light absorbing pigment,        dye or photochromic material;    -   optionally, at least one catalyst;    -   optionally, at least one filler;    -   the prepolymer accounts for 0 to 80% by weight of the hybrid        formulation composition, and the poly-ols account for 10 to 30%        by weight of the hybrid formulation composition.

The prepolymer containing a reactive diisocyanate is a compound of theformula T-R-T, and each T is a terminal group of R; wherein T is areactive isocyanate (NCO). R of the prepolymer further comprises areactive end group, or R of the prepolymer does not comprise a reactiveend group. In one embodiment, R is a network structure of a urethanepolymer.

Isocyanate (NCO) has high reactivity, especially aromatic isocyanate(NCO), so special attention should be paid to storage and processingapplications. Traditionally, it must be completely closed duringstorage. The Mole ratio should be adjusted appropriately in accordancewith moisture and temperature. The principle of blocked isocyanates isIsocyanates is one of the basic raw materials for the manufacture ofcoatings. Traditionally, the reaction between isocyanates and polyolshas been counteracted by blocking the isocyanate group, preventing thisreaction from occurring at room temperature. This allows the reaction tobe initiated at high temperatures. In the coatings industry, blockedisocyanates are one of the most effective ingredients in theformulation. These blocking agents are usually based onmethylethylketoxime, caprolactum and ethyl malonate.

In one embodiment, the prepolymer is passed through a polyisocyanateoligomer, a diisocyanate and/or a chain extender with an aminemethacrylate, an alcohol methacrylate, a maleic acid ester as adiisocyanate and/or a chain extender. The reaction of the imine orN-vinylformamide monomer blocking agent is blocked (i.e., the reactionproduct of the reaction between them). That is, the ratio of blockedisocyanate (NCO) to polyalcohol is usually measured by NCO:OH=1:1.However, blocked isocyanate (NCO) coatings will cure at a highertemperature.

In the present invention, isocyanate (NCO) is not blocked. The endgroups of the prepolymer may optionally comprise at least one single ormultiple ethylenic unsaturated end groups. The prepolymer comprises apolyisocyanate oligomer produced by reacting at least one isocyanate,with at least one polyol, and the ratio of the isocyanate to the polyol(NCO/OH) is greater than 1, that is, the isocyanate (NCO) is notblocked. That is, when the prepolymer is further disposed, the simpleisocyanate (NCO) monomer and the polyol are first reacted to form theprepolymer, and the isocyanate is retained in the prepolymer to a weightratio of 5% to 20% (NCO) content, not blocked.

These isocyanates are usually di- or tri-functional, with polyhydroxycompounds (polyols that are normally-OH terminated polyesters polyetheror acrylics). A network structure that reacts to form a urethane polymerin the presence of a suitable catalyst (usually in the presence of a tincom-plex).

The photocurable material formulation accounts for 20 to 100% by weightof the mixed formulation composition, and the photocurable materialcomprises at least: an acrylic series oligomer, an acrylic seriesmonomer, and at least one photoinitiator.

The acrylic series oligomer is selected from one of the followingcombinations: epoxy acrylate (EA), polyurethane acrylate (PUA),polyester acrylate (PEA), epoxy resin, unsaturated polyester, polyetheracrylate, and acrylate. The acrylic series oligomer content is from 0 to70% by weight based on the total weight of the photocurable material.The acrylic series oligomer is a polyurethane acrylate (PUA) forachieving a better curing effect; and the acrylic series oligomercontent is 0-60% by weight based on the total weight of the photocurablematerial; more preferably, the acrylic series oligomer content is from45 to 55 wt % of the total weight of the photocurable material.

The acrylic series monomer is selected from one of the followingcombinations: (meth) acrylate oxime, vinyl oxime, vinyl ether oxime,epoxy oxime. The acrylic series is selected from one of the followingcombinations: Trimethylopropane Formal Acrylate (CTFA), hydroxyethylmethacrylate (HEMA), β-carboxyethyl acrylates (β-CEA), IsobornylAcrylate (IBOA), 2-phenoxyethyl acrylate Ester (PHEA), 1,6-hexanedioldiacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), tripropyleneglycol diacrylate (TPGDA), trimethylol propane triacrylate (TMPTA),ethoxylated trimethylolpropane triacrylate [TMP(EO)TA], pentaerythritoltetraacrylate (PETTA), Trimethylolpropane tetraacrylate (DTEMPTTA),dipentaerythritol pentaacrylate (DPEPA), dipentaerythritol hexaacrylate,(DPHA), 2-Phenoxy Ethyl Acrylate (PHEA), Ortho-Phenyl Phenoxy EthylAcrylate (OPPEA), Benzyl Mathacrylate (BMA), 2-Phenoxy Ethyl Mehacrylate(PHEMA), N, N-Dimethyl acrylamide (DMAA), Acryloyl morpholine (ACMO), N,N-Diethyl acrylamide (DEAA) and its ethoxylation product. The acrylicseries monomer content is 30-70% by weight based on the total weight ofthe photocurable material. The acrylic series monomer is characterizedby a benzene ring or an amide (Amide) type amide, which can make thephotocurable material have better solubility; preferably, the acrylicmonomer content is 30-60% by weight of the total amount of thephotocurable material formulation. more preferably, the acrylic monomercontent is 45-55 wt % of the total weight of the photocurable materialformulation.

The photoinitiator is 1-Hydroxy-cyclohexyl-phenyl-ketone (184), Diphenyl(2,4,6-trimethylbenzoyl)-phosphineoxide (TPO),2-Hydroxy-2-methyl-1-phenyl-1-propanone (1173),2-Methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanonePhosphine oxide, Phenyl bis(2,4,6-trimethyl benzoyl,2-Benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone). Thephotoinitiator is contained in an amount of 0.01 to 10% by weight basedon the total weight of the photocurable material formulation;preferably, the photoinitiator is contained in an amount of 0.01 to 5%by weight based on the total weight of the photocurable materialformulation; more preferably, the photo initiator is 0.01 to 3% byweight based on the total weight of the photocurable material.

The photocurable material formulation may further comprise an additiveselected from the group consisting of a light stabilizer, a hardener, aleveling agent and a defoamer. After the additive is added to thephotocurable material, the photocurable material can stabilize the colorof the light after the illumination, rapidly solidify and smooth thesurface, and remove bubbles in the material. The content of the additiveis 0.01-40% by weight based on the total weight of the photocurablematerial formulation; preferably, the content of the additive is0.01-20% by weight based on the total weight of the photocurablematerial formulation; more preferably, the content of the additive is0.1-10% based on the total weight of the photocurable materialformulation.

The pigment, dye or photochromic material comprises from accounts for 0to 12% by weight of the mixed formulation composition, and the pigment,dye or photochromic material is selected from the group consisting oforganic pigments, inorganic dyes, titanium dioxide or carbon black. Thephotochromic material features a colorless or extremely light colorationwhen exposed to no light and produces significant color development uponillumination. The photochromic material is selected from the groupconsisting of fulgides, Schiff bases, phenoxy hydrazines,dihydropyrroles, naphthopyrans, benzopyrans, spiropyrans orspirooxazines. Preferably, the photochromic material is selected fromthe group consisting of benzopyran and spiropyran, which can have bettersolubility in the prepared acrylic series oligomers and acrylic seriesmonomers of the present invention for photochromic effect. Preferably,the pigment, dye or photochromic material is: (i) titanium dioxide, inan amount of from 0.05 to 12% by weight of the hybrid formulationcomposition, (ii) carbon black, of the hybrid formulation composition anamount of 0.05 to 10% by weight, (iii) an organic ultraviolet lightabsorber such as hydroxybenzophenone, hydroxyphenylbenzotriazole, oxalicaniline, benzophenone, hydroxyphenyl triazine and/or a benzotriazoleultraviolet light absorber, in an amount of 0.001 to 2% by weight of thehybrid formulation composition, and/or (iv) a combination of benzopyranand spiropyran, which constitutes the hybrid formulation composition anamount of 0.05 to 10% by weight.

The filler accounts for 0 to 40% by weight of the hybrid formulationcomposition. The filler is selected from the group consisting ofinorganic ore, calcium carbonate, cerium oxide, aluminum hydroxide,cerium oxide, halogen-containing or non-halogen fire-retardant material.

In the presence of a suitable catalyst (usually tin com-plex), theisocyanate reacts with a poly hydrocarbyl group (containing anOH-terminated polyester, a polyether or an acrylic polyol) to form aurethane. The network structure of the polymer. Preferably, the catalystin the amount of 0 to 1% by weight of the mixed formulation composition,and the catalyst is selected from the group consisting of aminecatalysts and metal catalysts.

The hybrid formulation composition may further comprise a reactivediluent for diluting the concentration and fluidity of the hybridformulation composition. The hybrid formulation composition may furthercomprise a secondary alcohol; more preferably secondary diol to extendthe pot life of the hybrid formulation composition.

The hybrid formulation composition 120 for 3D additive manufacturing hasrubber-like properties, which can increase the toughness, resilience andtear resistance of the structural material after curing, and can be usedfor shoe materials, toys, biomedical equipment, and wearable articles.

Referring to FIG. 2 together with FIG. 1, a first embodiment flow chartof a method for preparing a hybrid formulation composition formanufacturing 3D printed parts according to the present invention willbe described. The hybrid formulation composition for producing a 3Dprinted parts is similar to the foregoing and will not be describedherein. The mixed formulation composition is used to prepare a 3Dstructure comprising polyurethane, polyurea, acrylic or copolymerthereof. The process method includes the following steps

-   -   Step 1: Prepare a prepolymer containing reactive isocyanate;    -   Step 2: Prepare a photocurable material formulation;    -   Step 3: Mixing the prepolymer with the photocurable material        formulation;    -   Step 4: Optionally, mixing a polyol, a reactive diluent, at        least one non-reactive light absorbing pigment, a dye or a        photochromic material, at least one catalyst and at least one        filler;    -   The prepolymer accounts for 0 to 80% by weight of the hybrid        formulation composition, and the polyol accounts for from 10 to        30% by weight of the hybrid formulation composition.

The prepolymer comprises a polyisocyanate oligomer produced by reactingat least one isocyanate, in particular a two part isocyanate, with atleast one poly-ol, and the ratio of the isocyanate to the polyol(NCO/OH) is greater than 1, that is, the isocyanate (NCO) is notblocked. That is, when the prepolymer is further disposed, the simpleisocyanate (NCO) monomer and the polyol are first reacted to form theprepolymer, and the isocyanate is retained in the prepolymer to a weightratio of 5% to 20% (NCO) content, not blocked.

Referring to FIG. 3 together with FIG. 1, a second embodiment flow chartof a method for preparing a hybrid formulation composition for 3Dadditive manufacturing according to the present invention will bedescribed. The hybrid formulation composition for producing a 3D printedparts is similar to the foregoing and will not be described herein. Theprocess method of the 3D structure. The process method includes thefollowing steps

-   -   Step 1: Print a 3D structure layer by layer on a 3D printer        using a hybrid formulation composition;    -   Step 2: During the layered printing process, an ultraviolet (UV)        light is applied;    -   Step 3: After stopping the layered printing process, perform a        heating process;    -   Wherein the hybrid formulation composition mainly comprises:        -   A prepolymer containing reactive isocyanate (NCO) which            comprises of poly-ols (di-ol, tri-ol), urea, urethane, and            isocyanates;        -   A photocurable material formulation;        -   a poly-ol;        -   optionally, at least one non-reactive light absorbing            pigment, dye or photochromic material;        -   optionally, at least one catalyst;        -   optionally, at least one filler;    -   The prepolymer accounts for 0 to 80% by weight of the hybrid        formulation composition, and the poly-ols account for 10 to 30%        by weight of the hybrid formulation composition.

In the step 2: UV light irradiation step, a UV light is irradiated ontothe mixed composition 120 to cure the mixed composition 120 over the 3Dstructure 110. An important feature of the present invention is that themixed composition 120 is cured by irradiation of a UV light. The UVlight has a wavelength between 240 nm and 450 nm. The irradiationintensity of the UV light is between 0.1 J/cm² and 1 J/cm². Theirradiation time of the UV light is between 0.5 seconds and 90 seconds.

It should be noted that the mixed formulation composition for 3Dadditive manufacturing is a fluid-like substance which can beappropriately heated when various materials are dissolved.

In the step 3: heating process, the heating temperature is between 30°C. and 200° C.; preferably, the heating temperature is between 80° C.and 150° C. Moreover, the heating process is performed between 30minutes and 16 hours; preferably, the heating process is between 30minutes and 1 hour. The 3D structural finished product made of thehybrid formulation composition has rubber-like properties, whereby theheating process can increase the toughness, resilience and tearresistance of the cured 3D structural material.

In the present invention, the ratio of the isocyanate to the poly-ol(NCO/OH) of the prepolymer of the hybrid formulation composition for the3D additive manufacturing—is greater than 1 i.e. isocyanates are notblocked. The invention has the following advantages:

-   1. The toughness, resilience and tear resistance of the hybrid    formulation composition for 3D additive manufacturing can be    adjusted according to requirements, and it is free of volatile    substances, and is a very environmentally friendly and    environmentally friendly material.-   2. The hybrid formulation composition for 3D additive manufacturing    has rubber-like properties, which can increase the toughness,    resilience and tear resistance of the structural material after    curing, and can be used for shoe materials, toys, biomedical    equipment, and wearable articles.-   3. The process of the hybrid formulation composition for 3D additive    manufacturing requires only 2-3 seconds of photocuring, low heat    curing temperature, short process time, saving process energy and    increasing productivity.

While the present invention has been described in its preferredembodiments, it is not intended to limit the scope of the invention, andvarious modifications and changes can be made without departing from thespirit and scope of the invention. As explained above, variousmodifications and variations can be made without departing from thespirit of the invention. Therefore, the scope of the invention isdefined by the scope of the appended claims.

[Symbol Description] 110 3D Printer 120 Hybrid formulation composition130 3D Structure

What is claimed is:
 1. A mixed (hybrid) formulation composition for 3Dadditive manufacturing, which mainly comprises: a prepolymer containingreactive isocyanate (NCO) which comprises of poly-ols (di-ol, tri-ol),urea, urethane, and isocyanates; a photocurable material formulation;optionally, a poly-ol; optionally, at least one non-reactive lightabsorbing pigment, dye or photochromic material; optionally, at leastone catalyst; optionally, at least one filler; the prepolymer accountsfor 0 to 80% by weight of the hybrid formulation composition, and thepoly-ols account for 10 to 30% by weight of the hybrid formulationcomposition.
 2. The hybrid formulation composition of claim 1, whereinthe prepolymer is a compound of the formula T-R-T, R is a polymer of apolyol, each T is a terminal group of R, and T is a reactive isocyanate(NCO).
 3. The hybrid formulation composition of claim 2, wherein R ofthe prepolymer comprises reactive end groups.
 4. The hybrid formulationcomposition according to any one of claim 3, wherein the prepolymercomprises a polyisocyanate oligomer produced by reacting at least oneisocyanate with at least one polyol, and the ratio of the isocyanate tothe polyol (NCO/OH) is greater than one.
 5. The hybrid formulationcomposition according to claim 1, wherein the photocurable materialformulation accounts for 20 to 100% by weight of the hybrid formulationcomposition, and the photocurable composition formulation comprises atleast: an acrylic series oligomer, acrylic series monomers, and at leastone photoinitiator.
 6. The hybrid formulation composition of claim 5,wherein the acrylic series oligomer is selected from one of thefollowing combinations: epoxy acrylate (EA), polyurethane acrylate(PUA), polyester acrylate (PEA), epoxy resin, unsaturated polyester,polyether acrylate, and acrylated polyacrylic resin.
 7. The hybridformulation composition of claim 5, wherein the acrylic series singlesystem is selected from one of the following combinations: (meth)acrylate group, vinyl group, vinyl ether group, epoxy group.
 8. Thehybrid formulation composition of claim 1, wherein the pigment, dye orphotochromic material accounts for 0 to 12% by weight of the hybridformulation composition, and the pigment, dye or photochromic materialis selected from organic pigments, inorganic dyes, titanium dioxide orcarbon black.
 9. The hybrid formulation composition according to claim1, wherein the filler is in an amount of from 0 to 40% by weight of thehybrid formulation composition, and the filler is selected from thegroup consisting of inorganic ore, calcium carbonate, silicon dioxide,aluminium hydroxide, antimony oxide, halogen-containing fire-resistantmaterials or non-halogen fire-resistant materials.
 10. The hybridformulation composition of claim 1, wherein the catalyst is in an amountfrom 0 to 1% by weight of the hybrid formulation composition, and thecatalyst is selected from the group consisting of an amine catalyst anda metal catalyst.
 11. A process for producing a hybrid formulationcomposition for 3D additive manufacturing, comprising the followingsteps: preparing a prepolymer containing reactive isocyanate; preparinga photocurable material formulation; mixing the prepolymer with thephotocurable material component formulation; optionally, mixing apoly-ol, a reactive diluent, at least one non-reactive light absorbingpigment, a dye or photochromic material, at least one catalyst and atleast one filler; the prepolymer accounts for 0 to 80% by weight of thehybrid formulation composition, and the polyol accounts for 10 to 30% byweight of the hybrid formulation composition.
 12. The process of claim11, wherein the prepolymer is a compound of the formula T-R-T, R is apolymer of a polyol, and each T is a terminal group of R; wherein T is areactive isocyanate (NCO).
 13. The process of claim 12, wherein R of theprepolymer comprises reactive end groups.
 14. The process according toany one of claim 13, wherein the prepolymer comprises a polyisocyanateoligomer produced by reacting at least one isocyanate with at least onepolyol, and the ratio of the isocyanate to the polyol (NCO/OH) isgreater than
 1. 15. The process of claim 11, wherein the photocurablematerial formulation accounts for 20 to 100% by weight of the hybridformulation composition, and the photocurable material comprises atleast: an acrylic series oligomer, an acrylic series monomer, and atleast one photoinitiator.
 16. The process according to claim 15, whereinthe acrylic series oligomer is selected from one of the followingcombinations: epoxy acrylate (EA), polyurethane acrylate (PUA),polyester acrylate (PEA), epoxy resin, unsaturated polyester, polyetheracrylate, and acrylated polyacrylic resin.
 17. The process method ofclaim 15, wherein the acrylic series single system is selected from oneof the following combinations: (meth) acrylate group, vinyl group, vinylether group, epoxy group.
 18. The process of claim 15, wherein thephotocurable material formulation further comprises an additive selectedfrom the group consisting of a light stabilizer, a hardener, a primaryleveling agent and a defoaming agent.
 19. The process of claim 11,wherein the pigment, dye or photochromic material is: (i) titaniumdioxide, in an amount of from 0.05 to 12% by weight of the hybridformulation composition, (ii) carbon black, accounting for an amount of0.05 to 10% by weight of the hybrid formulation composition, (iii) anorganic ultraviolet light absorber such as hydroxybenzophenone,hydroxyphenylbenzotriazole, oxalic anilide, benzophenone, hydroxy aphenyltriazine and/or benzotriazole ultraviolet light absorber, in anamount of from 0.001 to 2% by weight of the hybrid formulationcomposition, and/or (iv) a combination of benzopyran and spiropyran, inan amount of from 0.05 to 10% by weight of the hybrid formulationcomposition.
 20. The process of claim 11, wherein the catalyst in theamount from 0 to 1% by weight of the mixed formulation composition, andthe catalyst is selected from the group consisting of amine catalystsand metal catalysts.